US20040058245A1 - Rechargeable battery - Google Patents
Rechargeable battery Download PDFInfo
- Publication number
- US20040058245A1 US20040058245A1 US10/239,745 US23974503A US2004058245A1 US 20040058245 A1 US20040058245 A1 US 20040058245A1 US 23974503 A US23974503 A US 23974503A US 2004058245 A1 US2004058245 A1 US 2004058245A1
- Authority
- US
- United States
- Prior art keywords
- active material
- alloyed
- particle
- metal element
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/49115—Electric battery cell making including coating or impregnating
Definitions
- the present invention relates to a rechargeable battery, and more specifically to a rechargeable battery which employs, as an active material, active material particles capable of being alloyed with Li.
- Li-alloy negative electrodes employing a metal capable of being alloyed with Li as well as carbon negative electrodes employing a carbon material such as graphite. Some of the carbon negative electrodes have been put to practical use.
- a rechargeable battery according to the present invention is a rechargeable battery which employs an electrode containing particles of an active material capable of being alloyed with Li, characterized in that a metal element incapable of being alloyed with Li is distributed by its diffusion into the active material particle.
- a concentration of the metal element incapable of being alloyed with Li increases from an interior of the active material particle toward a surface of the active material particle.
- a concentration of the metal element incapable of being alloyed with Li decreases from an interior of the active material particle toward a surface of the active material particle.
- the active material particle capable of being alloyed with Li is not limited to a specific one as long as it is made of a material capable of being alloyed with Li. From a viewpoint of obtaining high electrode capacity, it is preferable that the active material particle is at least one selected from Si, Ge, Sn, Al and In. Si is more preferable since it has a high theoretical capacity.
- the metal element incapable of being alloyed with Li which is diffused into the active material particle is not limited to a specific one as long as it is a metal element incapable of being alloyed with Li. It is, however, preferable that the metal element is a material having an excellent conductive property. From this viewpoint, Cu is particularly preferable.
- the rechargeable battery is characterized in that the active material particle substantially consists of Si and the metal element is Cu.
- the active material particle according to the present invention can be used as either a negative electrode active material or a positive electrode active material.
- the standard potential of the active material capable of being alloyed with Li relative to lithium metal is generally low, so that the active material particle of the present invention is considered to be used as a negative electrode active material in general.
- An electrode active material is generally produced by binding a powdery active material using a binder. Therefore, a location in which electrode reaction occurs is the powder itself as an active material. If Li is absorbed by the powdery active material, Li is absorbed from the surface of the powder first. In general, if Li is absorbed an active material and alloys with the active material, the volume expands so that the surface of the powder expands. However, since Li does not enter the interior of the active material, the interior of the active material does not expand. Therefore, the ratio of expansion of the surface greatly differs from that of the interior, with the result that the powder is pulverized. By adjusting the difference in expansion ratio between the surface and the interior, it is possible to suppress the active material from being pulverized. According to the present invention, by distributing the metal element incapable of being alloyed with Li by its diffusion into the active material particle, the difference in expansion ratio between the surface and the interior is decreased to suppress the particle from being pulverized.
- the concentration of the metal element incapable of being alloyed with Li is high and the concentration of the active material is low. Due to this, even if Li is absorbed by the active material, the expansion ratio of the surface of the active material is low and the difference in expansion ratio between the surface and the interior in which Li is not absorbed is not so great. Therefore, an internal stress decreases, making it possible to suppress the active material particle from being cracked.
- the concentration profile in which the metal element decreases from the interior toward the surface of the active material particle is high. Therefore, the surface greatly expands and the interior expands less, thereby increasing an internal stress.
- the concentration of the active material is low in the interior of the particle, so that the crack formed at the surface of the particle does not reach the interior thereof and only the surface of the particle cracks. As a result, the particle is not pulverized as a whole and kept in a state in which the particle is suppressed from being pulverized.
- various methods may be considered as methods of manufacturing an active material particle in which the concentration of the metal element incapable of being alloyed with Li increases from the interior toward the surface of the active material particle. They include, for example, the following methods:
- Si powder is used as the active material particle capable of being alloyed with Li and Cu is used as the metal element, then a Cu layer is formed on the surface of the Si powder by electroless plating, a heat treatment is then conducted to thereby diffuse Cu into the Si powder and it is possible to provide a concentration profile in which the concentration of Cu continuously increases from the interior toward the surface of the Si powder.
- Si powder is used as the active material particle capable of being alloyed with Li and Cu is used as the metal element, then the Si powder is mechanically mixed with Cu fine particle, a Cu layer is formed on the surface of the Si powder by the mechano-fusion method, a heat treatment is then conducted at an appropriate temperature to thereby diffuse Cu into the Si powder and it is possible to provide a concentration profile in which the concentration of Cu continuously increases from the interior toward the surface of the Si powder.
- various methods may be considered as methods of manufacturing an active material particle in which the concentration of the metal element incapable of being alloyed with Li decreases from the interior toward the surface of the active material particle capable of being alloyed with Li. They include, for example, the following methods:
- the active material particle can be produced by such a method.
- Si is used as the active material capable of being alloyed with Li and Cu is used as the metal element incapable of being alloyed with Li, then Cu powder and Si fine particle are mechanically mixed with each other, an Si layer is formed on the Cu powder by the mechano-fusion method, a heat treatment is conducted at an appropriate temperature to thereby diffuse Si into the Cu powder and it is possible to provide a concentration profile in which Cu decreases from the interior toward the surface of the particle.
- Si is used as the active material capable of being alloyed with Li and Cu is used as the metal element incapable of being alloyed with Li
- an SiO layer or an SiO 2 layer is formed on the Cu powder by the mechano-fusion method or the like, this oxide is reduced at an appropriate temperature in a reducing atmosphere such as hydrogen airflow and, at the same time, Si formed by reduction is diffused into the Cu particle and it is possible to provide a concentration profile in which the concentration of Cu decreases from the interior of the particle toward the surface thereof.
- the temperature of the heat treatment conducted to diffuse the metal element is preferably within a range of temperature raised from room temperature by about 1/10 to 4/5 of the melting point of the metal to be diffused with reference to the absolute temperature.
- FIG. 1 shows a Cu concentration profile obtained by SIMS analysis after subjecting a heat treatment to an Si film formed on a Cu foil.
- this Si powder was immersed into an electroless plating bath being adjusted to have a pH of 12.5 and having the composition shown in Table 2, until the surface of the Si powder is Cu-colored.
- TABLE 2 Substance Concentration Copper Sulfate 7.5 g ⁇ dm ⁇ 3 Rochelle Salt 85 g ⁇ dm ⁇ 3 Formaldehyde 22 cm 3 ⁇ dm ⁇ 3 Stabilizer (Methanol) 7.5%
- FIG. 1 shows this result.
- Cu is present in the Si thin film and diffused into the Si thin film.
- Cu increases from the interior of the Si thin film toward the surface thereof. Accordingly, it is understood that the Si powder also has Cu diffused thereinto and has a Cu concentration profile that the concentration of Cu increases from the interior of the Si powder toward the surface thereof.
- the working electrode and the counter electrode produced as stated above were superposed on each other through a polypropylene separator, the superposed electrodes were put between glass plates and immersed into an electrolyte, thereby producing a test cell.
- the Li metal was immersed into the electrolyte so as not to contact with these electrodes, and was employed as a reference electrode.
- As the electrolyte a solution obtained by dissolving 1 mol/litter of LiPF 6 into a mixed solvent of ethylene carbonate and diethyl carbonate in equivalent volume was employed.
- a comparative test cell was produced in the same manner as that of the above-stated test cell except that 100 g of Si powder having an average particle diameter of 1 ⁇ m was used as a negative electrode active material as it is. The obtained cell was referred to as Comparative Battery A.
- a comparison test cell was also produced as in the same manner as that of the above-stated test cell except that 100 g of copper silicide powder having an average particle diameter of 1 ⁇ m was used as a negative electrode active material as it is. The obtained cell was referred to as Comparative Battery B.
- a charge-discharge cycle test was conducted to each test cell. Each cell was charged to 0V with Li reference, discharged to 2V with Li reference and a charge-discharge current was 0.5 mA. Table 3 shows the discharge capacity and charge-discharge efficiency of each test cell.
- Inventive Battery exhibited high discharge capacity and good charge-discharge efficiency even if the number of cycles increases, compared with Comparison Batteries A and B.
- the test cells after 10 cycles were decomposed for investigation.
- the negative electrode active material in the test cell was slightly separated from the Cu foil serving as a current collector, while the shape of the negative electrode active material was kept.
- the comparison batteries A and B by contrast, most of the negative electrode active material was separated from the current collector, and the shape of the negative electrode active material itself was not kept. The active material was pulverized and most of then fell off and were dispersed the electrolyte.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
- The present invention relates to a rechargeable battery, and more specifically to a rechargeable battery which employs, as an active material, active material particles capable of being alloyed with Li.
- Attention has been paid to a lithium rechargeable battery which employs a lithium metal as a negative electrode, as a next generation rechargeable battery because of its high energy density. However, since the lithium metal is employed for the negative electrode, the lithium metal is dissolved and deposited during charge and discharge, thereby producing dendrites and deforming the electrode. For that reason, this type of lithium rechargeable battery is inferior in cycle characteristic and cannot be put to practical use. To solve such a problem, proposed are Li-alloy negative electrodes employing a metal capable of being alloyed with Li as well as carbon negative electrodes employing a carbon material such as graphite. Some of the carbon negative electrodes have been put to practical use.
- Nevertheless, since the theoretical capacity of the carbon negative electrode is as low as 372 mAh/g, the energy density of the carbon negative electrode is disadvantageously low compared with the negative electrode which employs the metal lithium. Furthermore, when the Li-alloy negative electrode is employed, expansion and shrinkage in volume are repeated during charge and discharge. Due to this, the active material particles are pulverized during charge-discharge cycles, thereby disadvantageously deteriorating the cycle characteristics of the battery.
- It is an object of the present invention to provide a rechargeable battery which employs an electrode containing particles of an active material capable of being alloyed with Li, which can suppress the active material particles from being pulverized and which can surprisingly improve the cycle characteristics of the battery.
- A rechargeable battery according to the present invention is a rechargeable battery which employs an electrode containing particles of an active material capable of being alloyed with Li, characterized in that a metal element incapable of being alloyed with Li is distributed by its diffusion into the active material particle.
- In the first aspect according to the present invention, a concentration of the metal element incapable of being alloyed with Li increases from an interior of the active material particle toward a surface of the active material particle.
- In the second aspect according to the present invention, a concentration of the metal element incapable of being alloyed with Li decreases from an interior of the active material particle toward a surface of the active material particle.
- In the present invention, the active material particle capable of being alloyed with Li is not limited to a specific one as long as it is made of a material capable of being alloyed with Li. From a viewpoint of obtaining high electrode capacity, it is preferable that the active material particle is at least one selected from Si, Ge, Sn, Al and In. Si is more preferable since it has a high theoretical capacity.
- In the present invention, the metal element incapable of being alloyed with Li which is diffused into the active material particle is not limited to a specific one as long as it is a metal element incapable of being alloyed with Li. It is, however, preferable that the metal element is a material having an excellent conductive property. From this viewpoint, Cu is particularly preferable.
- Accordingly, in a preferred embodiment according to the present invention, the rechargeable battery is characterized in that the active material particle substantially consists of Si and the metal element is Cu.
- The active material particle according to the present invention can be used as either a negative electrode active material or a positive electrode active material. However, the standard potential of the active material capable of being alloyed with Li relative to lithium metal is generally low, so that the active material particle of the present invention is considered to be used as a negative electrode active material in general.
- (Effect and Advantage)
- An electrode active material is generally produced by binding a powdery active material using a binder. Therefore, a location in which electrode reaction occurs is the powder itself as an active material. If Li is absorbed by the powdery active material, Li is absorbed from the surface of the powder first. In general, if Li is absorbed an active material and alloys with the active material, the volume expands so that the surface of the powder expands. However, since Li does not enter the interior of the active material, the interior of the active material does not expand. Therefore, the ratio of expansion of the surface greatly differs from that of the interior, with the result that the powder is pulverized. By adjusting the difference in expansion ratio between the surface and the interior, it is possible to suppress the active material from being pulverized. According to the present invention, by distributing the metal element incapable of being alloyed with Li by its diffusion into the active material particle, the difference in expansion ratio between the surface and the interior is decreased to suppress the particle from being pulverized.
- In the first aspect of the present invention, provided is a concentration profile in which the metal element incapable of being alloyed with Li increases from the interior toward the surface of the active material particle. In this case, on the surface, the concentration of the metal element incapable of being alloyed with Li is high and the concentration of the active material is low. Due to this, even if Li is absorbed by the active material, the expansion ratio of the surface of the active material is low and the difference in expansion ratio between the surface and the interior in which Li is not absorbed is not so great. Therefore, an internal stress decreases, making it possible to suppress the active material particle from being cracked.
- In the second aspect of the present invention, provided is a concentration profile in which the metal element decreases from the interior toward the surface of the active material particle. In this case, the concentration of the active material on the surface of the particle is high. Therefore, the surface greatly expands and the interior expands less, thereby increasing an internal stress. However, the concentration of the active material is low in the interior of the particle, so that the crack formed at the surface of the particle does not reach the interior thereof and only the surface of the particle cracks. As a result, the particle is not pulverized as a whole and kept in a state in which the particle is suppressed from being pulverized.
- According to the first aspect of the present invention, various methods may be considered as methods of manufacturing an active material particle in which the concentration of the metal element incapable of being alloyed with Li increases from the interior toward the surface of the active material particle. They include, for example, the following methods:
- (1) A method of providing a layer of a metal element incapable of being alloyed with Li on the surface of an active material particle capable of being alloyed with Li by electroless plating and then heat treating the active material particle at an appropriate temperature to thereby diffuse the metal element from the surface into the interior of the active material particle.
- If Si powder is used as the active material particle capable of being alloyed with Li and Cu is used as the metal element, then a Cu layer is formed on the surface of the Si powder by electroless plating, a heat treatment is then conducted to thereby diffuse Cu into the Si powder and it is possible to provide a concentration profile in which the concentration of Cu continuously increases from the interior toward the surface of the Si powder.
- (2) A method of providing a layer of a metal element incapable of being alloyed with Li on the surface of an active material particle capable of being alloyed with Li by a mechano-fusion method and then heat treating the active material particle at an appropriate temperature to thereby diffuse the metal element from the surface into the interior of the active material particle.
- If Si powder is used as the active material particle capable of being alloyed with Li and Cu is used as the metal element, then the Si powder is mechanically mixed with Cu fine particle, a Cu layer is formed on the surface of the Si powder by the mechano-fusion method, a heat treatment is then conducted at an appropriate temperature to thereby diffuse Cu into the Si powder and it is possible to provide a concentration profile in which the concentration of Cu continuously increases from the interior toward the surface of the Si powder.
- According to the second aspect of the present invention, various methods may be considered as methods of manufacturing an active material particle in which the concentration of the metal element incapable of being alloyed with Li decreases from the interior toward the surface of the active material particle capable of being alloyed with Li. They include, for example, the following methods:
- (3) A method of providing a layer of an active material capable of being alloyed with Li on the surface of a metal particle incapable of being alloyed with Li by electroless plating and then heat treating the metal particle at an appropriate temperature.
- For example, if Ge is used as the active material capable of being alloyed with Li and Cu is used as the metal element incapable of being alloyed with Li, the active material particle can be produced by such a method.
- (4) A method of providing a layer of an active material capable of being alloyed with Li on the surface of a metal particle incapable of being alloyed with Li by a mechano-fusion method and heat treating the metal particle at an appropriate temperature.
- If Si is used as the active material capable of being alloyed with Li and Cu is used as the metal element incapable of being alloyed with Li, then Cu powder and Si fine particle are mechanically mixed with each other, an Si layer is formed on the Cu powder by the mechano-fusion method, a heat treatment is conducted at an appropriate temperature to thereby diffuse Si into the Cu powder and it is possible to provide a concentration profile in which Cu decreases from the interior toward the surface of the particle.
- (5) A method of providing a layer of an oxide of an active material on the surface of a metal particle incapable of being alloyed with Li by a mechano-fusion method or the like, then reducing the oxide at an appropriate temperature in a reducing atmosphere such as hydrogen airflow and also diffusing this reduced active material into the metal particle.
- If Si is used as the active material capable of being alloyed with Li and Cu is used as the metal element incapable of being alloyed with Li, then an SiO layer or an SiO2 layer is formed on the Cu powder by the mechano-fusion method or the like, this oxide is reduced at an appropriate temperature in a reducing atmosphere such as hydrogen airflow and, at the same time, Si formed by reduction is diffused into the Cu particle and it is possible to provide a concentration profile in which the concentration of Cu decreases from the interior of the particle toward the surface thereof.
- In case of methods (1) to (5) stated above, the temperature of the heat treatment conducted to diffuse the metal element is preferably within a range of temperature raised from room temperature by about 1/10 to 4/5 of the melting point of the metal to be diffused with reference to the absolute temperature.
- FIG. 1 shows a Cu concentration profile obtained by SIMS analysis after subjecting a heat treatment to an Si film formed on a Cu foil.
- The present invention is below described in more detail by way of Examples. It will be recognized that the following examples merely illustrate the particle of the present invention but are not intended to be limiting thereof. Suitable changes and modifications can be effected without departing from the scope of the present invention.
- [Production of Battery of the Present Invention]
- [Production of Negative Electrode Active Material]
- 100 g of Si powder having an average particle diameter of 1 μm was immersed into 500 cc of an aqueous solution having a composition as shown in Table 1 at a temperature of 35° C. for 3 minutes, and then washed and immersed into 10% by volume of an HCl aqueous solution for 5 minutes, thereby forming Pd nuclei serving as a catalyst for electroless plating on the surface of the Si powder.
TABLE 1 Substance Chemical Formula Concentration Palladium Chloride PdCl2 · 2H2O 0.2 g · dm−3 Stannous Chloride SnCl2 · 2H20 15 g · dm−3 Concentrated HCl 200 cm3 · dm−3 Hydrochloric Acid - Next, this Si powder was immersed into an electroless plating bath being adjusted to have a pH of 12.5 and having the composition shown in Table 2, until the surface of the Si powder is Cu-colored. The Si powder on the surface of which a Cu layer was thus formed, was subjected to a heat treatment at 500° C. in vacuum, thereby diffusing Cu into the Si powder.
TABLE 2 Substance Concentration Copper Sulfate 7.5 g · dm−3 Rochelle Salt 85 g · dm−3 Formaldehyde 22 cm3 · dm−3 Stabilizer (Methanol) 7.5% - To examine that Cu was diffused into the Si powder as a result of the heat treatment, an Si film having a thickness of 2 μm, instead of the Si powder, was formed on a Cu foil by the CVD method, and subjected to a heat treatment. It was confirmed that Cu was diffused into the Si thin film by SIMS analysis. FIG. 1 shows this result. As shown in FIG. 1, Cu is present in the Si thin film and diffused into the Si thin film. In addition, as shown in FIG. 1, Cu increases from the interior of the Si thin film toward the surface thereof. Accordingly, it is understood that the Si powder also has Cu diffused thereinto and has a Cu concentration profile that the concentration of Cu increases from the interior of the Si powder toward the surface thereof.
- (Production of Working Electrode)
- 100 g of the negative electrode active material produced above was mixed with an N-methyl-pyrrolidone solution which fluororesin (PVdF), serving as a binder, is dissolved to have a concentration of 5%, the resultant mixture was smashed and mixed with a smash and mixing machine for 30 minutes to thereby prepare a slurry. This slurry was applied on an electrolytic copper foil having a thickness of 18 μm by the doctor blade technique, dried and cut into dimensions of 2×2 cm, thereby obtaining a working electrode.
- (Production of Counter Electrode)
- An Li metal having a thickness of 0.9 mm was cut into dimensions of 3×3 cm, thereby obtaining a counter electrode.
- (Production of Test Cell)
- The working electrode and the counter electrode produced as stated above were superposed on each other through a polypropylene separator, the superposed electrodes were put between glass plates and immersed into an electrolyte, thereby producing a test cell. The Li metal was immersed into the electrolyte so as not to contact with these electrodes, and was employed as a reference electrode. As the electrolyte, a solution obtained by dissolving 1 mol/litter of LiPF6 into a mixed solvent of ethylene carbonate and diethyl carbonate in equivalent volume was employed.
- [Production of Comparative Battery]
- A comparative test cell was produced in the same manner as that of the above-stated test cell except that 100 g of Si powder having an average particle diameter of 1 μm was used as a negative electrode active material as it is. The obtained cell was referred to as Comparative Battery A. A comparison test cell was also produced as in the same manner as that of the above-stated test cell except that 100 g of copper silicide powder having an average particle diameter of 1 μm was used as a negative electrode active material as it is. The obtained cell was referred to as Comparative Battery B.
- [Charge-Discharge Cycle Test]
- A charge-discharge cycle test was conducted to each test cell. Each cell was charged to 0V with Li reference, discharged to 2V with Li reference and a charge-discharge current was 0.5 mA. Table 3 shows the discharge capacity and charge-discharge efficiency of each test cell.
TABLE 3 Inventive Battery Comparative Comparative Charge Battery A Battery B Dis- Dis- Dis- charge charge charge Charge- Charge- Number Capac- Effi- Capac- Discharge- Discharge Discharge of ity ciency ity Efficiency Capacity Efficiency Cycles mAh/g % mAh/g % mAh/ g % 1 2000 91 640 21 610 48 2 1990 99 320 50 450 74 5 1950 98 150 82 350 87 10 1930 97 130 82 295 87 - As shown in Table 3, Inventive Battery exhibited high discharge capacity and good charge-discharge efficiency even if the number of cycles increases, compared with Comparison Batteries A and B. The test cells after 10 cycles were decomposed for investigation. In case of battery of the present invention, the negative electrode active material in the test cell was slightly separated from the Cu foil serving as a current collector, while the shape of the negative electrode active material was kept. In case of the comparison batteries A and B, by contrast, most of the negative electrode active material was separated from the current collector, and the shape of the negative electrode active material itself was not kept. The active material was pulverized and most of then fell off and were dispersed the electrolyte.
- As can be understood from the above, in the battery of the present invention, pulverization of the active material is not caused by charge-discharge cycle test and therefore the battery of the present invention exhibits excellent cycle characteristics.
- According to the present invention, it is possible to suppress active material particles from being pulverized and to greatly improve cycle characteristics.
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/979,915 US7655273B2 (en) | 2000-03-28 | 2007-11-09 | Method of manufacturing an electrode active material particle for a rechargeable battery |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000-89272 | 2000-03-28 | ||
JP2000089272A JP4229567B2 (en) | 2000-03-28 | 2000-03-28 | Secondary battery |
PCT/JP2001/002048 WO2001073872A1 (en) | 2000-03-28 | 2001-03-15 | Rechargeable battery |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/979,915 Division US7655273B2 (en) | 2000-03-28 | 2007-11-09 | Method of manufacturing an electrode active material particle for a rechargeable battery |
Publications (2)
Publication Number | Publication Date |
---|---|
US20040058245A1 true US20040058245A1 (en) | 2004-03-25 |
US7316717B2 US7316717B2 (en) | 2008-01-08 |
Family
ID=18605049
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/239,745 Expired - Lifetime US7316717B2 (en) | 2000-03-28 | 2001-03-15 | Method of manufacturing an electrode active material particle for a rechargeable battery |
US11/979,915 Expired - Fee Related US7655273B2 (en) | 2000-03-28 | 2007-11-09 | Method of manufacturing an electrode active material particle for a rechargeable battery |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/979,915 Expired - Fee Related US7655273B2 (en) | 2000-03-28 | 2007-11-09 | Method of manufacturing an electrode active material particle for a rechargeable battery |
Country Status (9)
Country | Link |
---|---|
US (2) | US7316717B2 (en) |
EP (1) | EP1271674B1 (en) |
JP (1) | JP4229567B2 (en) |
KR (1) | KR100483408B1 (en) |
CN (1) | CN1241278C (en) |
AU (1) | AU2001241149A1 (en) |
DE (1) | DE60142778D1 (en) |
HK (1) | HK1053390A1 (en) |
WO (1) | WO2001073872A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040253518A1 (en) * | 2003-04-11 | 2004-12-16 | Yosuke Hosoya | Positive active material and nonaqueous electrolyte secondary battery produced using the same |
US20050118502A1 (en) * | 2003-11-27 | 2005-06-02 | Matsushita Electric Industrial Co., Ltd. | Energy device and method for producing the same |
US20060040182A1 (en) * | 2003-03-26 | 2006-02-23 | Canon Kabushiki Kaisha | Electrode material for lithium secondary battery and electrode structure having the electrode material |
US20060115735A1 (en) * | 2003-04-23 | 2006-06-01 | Kiyotaka Yasuda | Negative electrode for nonaqueous electrolyte secondary battery, method for manufacturing same and nonaqueous electrolyte secondary battery |
US20060121345A1 (en) * | 2003-12-04 | 2006-06-08 | Kiyotaka Yasuda | Electrode for secondary battery, process of producing the electrode, and secondary battery |
US20090169985A1 (en) * | 2007-12-26 | 2009-07-02 | Sony Corporation | Electrolytic solution, secondary battery and method of manufacturing same, and sulfone compound |
US20110183208A1 (en) * | 2006-02-07 | 2011-07-28 | Panasonic Corporation | Negative-electrode active material for nonaqueous electrolyte secondary battery, and negative electrode and nonaqueous electrolyte secondary battery using the same |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1280930C (en) * | 2000-09-01 | 2006-10-18 | 三洋电机株式会社 | Negative electrode for lithium secondary cell and method for producing the same |
EP1313158A3 (en) | 2001-11-20 | 2004-09-08 | Canon Kabushiki Kaisha | Electrode material for rechargeable lithium battery, electrode comprising said electrode material, rechargeable lithium battery having said electrode , and process for the production thereof |
JP2005197080A (en) * | 2004-01-07 | 2005-07-21 | Nec Corp | Anode for secondary battery and secondary battery using it |
JP2005293852A (en) * | 2004-03-31 | 2005-10-20 | Sanyo Electric Co Ltd | Manufacturing method of lithium secondary battery and anode for the lithium secondary battery |
JP4953610B2 (en) | 2005-09-29 | 2012-06-13 | 三洋電機株式会社 | Lithium secondary battery |
CN101292379B (en) * | 2005-11-08 | 2012-04-18 | 三井金属矿业株式会社 | Negative electrode for nonaqueous electrolyte secondary battery |
US8951672B2 (en) | 2007-01-30 | 2015-02-10 | Sony Corporation | Anode, method of manufacturing it, battery, and method of manufacturing it |
JP5245425B2 (en) * | 2007-06-05 | 2013-07-24 | ソニー株式会社 | Negative electrode and secondary battery |
JP5520538B2 (en) * | 2009-08-03 | 2014-06-11 | 古河電気工業株式会社 | Negative electrode material for lithium ion secondary battery containing nano-sized particles, negative electrode for lithium ion secondary battery, lithium ion secondary battery |
KR101702987B1 (en) * | 2009-11-04 | 2017-02-23 | 삼성에스디아이 주식회사 | Negative electrode for rechargeable lithium battery and rechargeable lithium battery including same |
JP2011165402A (en) | 2010-02-05 | 2011-08-25 | Sony Corp | Anode for lithium ion secondary battery, lithium ion secondary battery, power tool, electric vehicle, and power storage system |
JP5581716B2 (en) | 2010-02-05 | 2014-09-03 | ソニー株式会社 | Negative electrode for lithium ion secondary battery, lithium ion secondary battery, electric tool, electric vehicle and power storage system |
JP5617265B2 (en) | 2010-02-05 | 2014-11-05 | ソニー株式会社 | Negative electrode for lithium ion secondary battery, lithium ion secondary battery, electric tool, electric vehicle and power storage system |
JP5187335B2 (en) * | 2010-03-29 | 2013-04-24 | 日本電気株式会社 | Negative electrode for secondary battery and method for producing the same, secondary battery |
US9356320B2 (en) * | 2012-10-15 | 2016-05-31 | Front Edge Technology Inc. | Lithium battery having low leakage anode |
JP6156190B2 (en) * | 2014-02-27 | 2017-07-05 | ソニー株式会社 | Negative electrode active material, battery, battery pack, electronic device, electric vehicle, power storage device, and power system |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4548507A (en) * | 1982-10-05 | 1985-10-22 | Mathis System-Technik Gmbh | Mixing apparatus for the production of mixtures |
US5149192A (en) * | 1988-09-30 | 1992-09-22 | Mixer Products, Inc. | System for mixing cementitious construction materials |
US5268111A (en) * | 1992-02-03 | 1993-12-07 | Metz Jeffrey L | Concrete reclamation system with mixing agitator |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07114124B2 (en) * | 1986-07-02 | 1995-12-06 | 日立マクセル株式会社 | Non-aqueous electrolyte secondary battery |
JPH03159075A (en) * | 1989-11-17 | 1991-07-09 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
JPH04259764A (en) * | 1991-02-12 | 1992-09-16 | Yuasa Corp | Lithium secondary battery |
DE69836514T2 (en) | 1997-01-28 | 2007-09-13 | Canon K.K. | Electrode body, provided with this accumulator, and production of the electrode body and the accumulator |
US6048644A (en) * | 1997-03-24 | 2000-04-11 | Matsushita Electric Industrial Co., Ltd. | Hydrogen storage alloy electrode |
JPH10308207A (en) | 1997-05-08 | 1998-11-17 | Matsushita Denchi Kogyo Kk | Non-aqueous electrolyte secondary battery |
JPH1186854A (en) | 1997-09-11 | 1999-03-30 | Hitachi Ltd | Lithium secondary battery |
JPH11102699A (en) | 1997-09-26 | 1999-04-13 | Asahi Chem Ind Co Ltd | Lithium secondary battery and negative electrode used therefor |
JPH11176470A (en) | 1997-10-07 | 1999-07-02 | Hitachi Maxell Ltd | Organic electrolyte secondary battery |
JPH11233108A (en) * | 1998-02-12 | 1999-08-27 | Hitachi Ltd | Lithium secondary battery |
JP3661417B2 (en) | 1998-06-18 | 2005-06-15 | 宇部興産株式会社 | Non-aqueous secondary battery |
JP3941235B2 (en) * | 1998-05-13 | 2007-07-04 | 宇部興産株式会社 | Non-aqueous secondary battery |
JP3627516B2 (en) * | 1998-06-08 | 2005-03-09 | 宇部興産株式会社 | Non-aqueous secondary battery |
KR100366978B1 (en) * | 1998-09-08 | 2003-01-09 | 마츠시타 덴끼 산교 가부시키가이샤 | Negative electrode material for nonaqueous electrode secondary battery and method for producing the same |
US6506520B1 (en) * | 1998-12-02 | 2003-01-14 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
US6605386B1 (en) * | 1998-12-02 | 2003-08-12 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery comprising composite particles |
JP2000173583A (en) | 1998-12-02 | 2000-06-23 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary battery |
JP4432130B2 (en) | 1998-12-02 | 2010-03-17 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery |
JP4457429B2 (en) | 1999-03-31 | 2010-04-28 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery and its negative electrode |
JP4416232B2 (en) * | 1999-11-16 | 2010-02-17 | 三菱化学株式会社 | Anode material for non-aqueous lithium secondary battery and non-aqueous lithium secondary battery using the same |
-
2000
- 2000-03-28 JP JP2000089272A patent/JP4229567B2/en not_active Expired - Fee Related
-
2001
- 2001-03-15 DE DE60142778T patent/DE60142778D1/en not_active Expired - Lifetime
- 2001-03-15 WO PCT/JP2001/002048 patent/WO2001073872A1/en active IP Right Grant
- 2001-03-15 AU AU2001241149A patent/AU2001241149A1/en not_active Abandoned
- 2001-03-15 EP EP01912387A patent/EP1271674B1/en not_active Expired - Lifetime
- 2001-03-15 KR KR10-2002-7012777A patent/KR100483408B1/en not_active IP Right Cessation
- 2001-03-15 US US10/239,745 patent/US7316717B2/en not_active Expired - Lifetime
- 2001-03-15 CN CNB018071775A patent/CN1241278C/en not_active Expired - Fee Related
-
2003
- 2003-08-01 HK HK03105538A patent/HK1053390A1/en not_active IP Right Cessation
-
2007
- 2007-11-09 US US11/979,915 patent/US7655273B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4548507A (en) * | 1982-10-05 | 1985-10-22 | Mathis System-Technik Gmbh | Mixing apparatus for the production of mixtures |
US5149192A (en) * | 1988-09-30 | 1992-09-22 | Mixer Products, Inc. | System for mixing cementitious construction materials |
US5268111A (en) * | 1992-02-03 | 1993-12-07 | Metz Jeffrey L | Concrete reclamation system with mixing agitator |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060040182A1 (en) * | 2003-03-26 | 2006-02-23 | Canon Kabushiki Kaisha | Electrode material for lithium secondary battery and electrode structure having the electrode material |
US20040253518A1 (en) * | 2003-04-11 | 2004-12-16 | Yosuke Hosoya | Positive active material and nonaqueous electrolyte secondary battery produced using the same |
US8062794B2 (en) * | 2003-04-11 | 2011-11-22 | Sony Corporation | Positive active material and nonaqueous electrolyte secondary battery produced using the same |
US20060115735A1 (en) * | 2003-04-23 | 2006-06-01 | Kiyotaka Yasuda | Negative electrode for nonaqueous electrolyte secondary battery, method for manufacturing same and nonaqueous electrolyte secondary battery |
US20050118502A1 (en) * | 2003-11-27 | 2005-06-02 | Matsushita Electric Industrial Co., Ltd. | Energy device and method for producing the same |
US20050118504A1 (en) * | 2003-11-27 | 2005-06-02 | Matsushita Electric Industrial Co., Ltd. | Energy device and method for producing the same |
US20060121345A1 (en) * | 2003-12-04 | 2006-06-08 | Kiyotaka Yasuda | Electrode for secondary battery, process of producing the electrode, and secondary battery |
US20110183208A1 (en) * | 2006-02-07 | 2011-07-28 | Panasonic Corporation | Negative-electrode active material for nonaqueous electrolyte secondary battery, and negative electrode and nonaqueous electrolyte secondary battery using the same |
US20090169985A1 (en) * | 2007-12-26 | 2009-07-02 | Sony Corporation | Electrolytic solution, secondary battery and method of manufacturing same, and sulfone compound |
Also Published As
Publication number | Publication date |
---|---|
HK1053390A1 (en) | 2003-10-17 |
AU2001241149A1 (en) | 2001-10-08 |
EP1271674A4 (en) | 2007-09-05 |
DE60142778D1 (en) | 2010-09-23 |
JP4229567B2 (en) | 2009-02-25 |
CN1419716A (en) | 2003-05-21 |
EP1271674B1 (en) | 2010-08-11 |
US20080226816A1 (en) | 2008-09-18 |
US7655273B2 (en) | 2010-02-02 |
CN1241278C (en) | 2006-02-08 |
US7316717B2 (en) | 2008-01-08 |
KR100483408B1 (en) | 2005-04-15 |
JP2001273892A (en) | 2001-10-05 |
EP1271674A1 (en) | 2003-01-02 |
KR20020086710A (en) | 2002-11-18 |
WO2001073872A1 (en) | 2001-10-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7655273B2 (en) | Method of manufacturing an electrode active material particle for a rechargeable battery | |
CN111628157B (en) | Positive electrode material, preparation method thereof and lithium ion battery | |
CN110010895B (en) | Carbon fiber loaded magnesium oxide particle cross-linked nanosheet array composite material and preparation method and application thereof | |
CN101222047B (en) | Cathode material of thin film lithium ion battery and method for producing the same | |
TW200941802A (en) | Mesoporous materials for electrodes | |
JP2007087789A (en) | Negative electrode for lithium ion secondary battery and its manufacturing method | |
CN112072076B (en) | Modification method for surface of negative electrode of lithium metal battery | |
WO2024148830A1 (en) | Secondary battery and battery pack | |
EP1110259B1 (en) | Nickel positive electrode having high-temperature capacity | |
CN115881892A (en) | Secondary battery and electric equipment | |
CN107749481B (en) | Preparation method of silicon-silver-carbon ternary composite material | |
CN111499995A (en) | Polymer composite membrane and preparation method thereof, composite electrode plate and preparation method thereof, and lithium metal secondary battery | |
CN114032532B (en) | Sodium metal battery current collector and preparation method and application thereof | |
CN116387511B (en) | Positive electrode material, preparation method thereof and battery | |
Zijian Zhao et al. | A Combined Lithium Intercalation and Plating Mechanism Using Conductive Carbon‐Fiber Electrodes | |
Zhao et al. | A Combined Li Intercalation and Plating Mechanism Using Conductive Carbon Fiber Electrodes | |
US6849359B1 (en) | Non-sintered nickel electrode for alkaline storage battery | |
CN116936763A (en) | Lithium-rich positive electrode material, preparation method thereof, positive electrode plate and secondary battery | |
CN116779877A (en) | Preparation method and application of molybdenum nitride coated copper nanowire/foam copper current collector with lithium-philic gradient | |
KR20220151327A (en) | Anode for lithium secondary battery comprising interfacial layer made of phosphorus-doped graphitic carbon nitride, lithium secondary battery comprising the same, and producing method thereof | |
JP2773253B2 (en) | Manufacturing method of cadmium negative electrode for alkaline storage battery | |
CN117133870A (en) | Preparation method, product and application of vertical multi-channel silicon electrode | |
CN111969213A (en) | Energy storage device positive electrode material, preparation method and modified energy storage device | |
CN114725334A (en) | Flower-like zinc selenide-manganese/carbon composite material and preparation method and application thereof | |
CN117995997A (en) | Negative electrode material of sodium ion battery and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: SANYO ELECTRIC CO., LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:FUJIMOTO, MASAHISA;KUSUMOTO, YASUYUKI;MIYAKE, MASAHIDE;AND OTHERS;REEL/FRAME:014487/0608 Effective date: 20021114 |
|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1553); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 12 |